WO2009061685A1 - Nano graphene platelet-based composite anode compositions for lithium ion batteries - Google Patents
Nano graphene platelet-based composite anode compositions for lithium ion batteries Download PDFInfo
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- WO2009061685A1 WO2009061685A1 PCT/US2008/082183 US2008082183W WO2009061685A1 WO 2009061685 A1 WO2009061685 A1 WO 2009061685A1 US 2008082183 W US2008082183 W US 2008082183W WO 2009061685 A1 WO2009061685 A1 WO 2009061685A1
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention provides a nano-scaled graphene platelet-based composite material for use as an anode active material in a secondary battery, particularly lithium-ion battery.
- the carbonaceous material may comprise primarily graphite that can be intercalated with lithium and the resulting graphite intercalation compound may be expressed as Li x Co, where x is typically less than 1.
- x in Li x Co must be maximized and the irreversible capacity loss Q s in the first charge of the battery must be minimized.
- Carbon anodes can have a long cycle life due to the presence of a protective surface-electrolyte interface layer (SEI), which results from the reaction between lithium and the electrolyte during the first several cycles of charge-discharge.
- SEI surface-electrolyte interface layer
- the lithium in this reaction comes from some of the lithium ions originally intended for the charge transfer purpose.
- the SEI As the SEI is formed, the lithium ions become part of the inert SEI layer and become irreversible, i.e, they can no longer be the active element for charge transfer. Therefore, it is desirable to use a minimum amount of lithium for the formation of an effective SEI layer.
- Q ⁇ r has been attributed to graphite exfoliation caused by electrolyte solvent co-intercalation and other side reactions [Refs.
- the amorphous phase typically can store lithium to a specific capacity level higher than 372 mAh/g, up to 700 mAh/g in some cases, although a specific capacity higher than 1 ,000 mAh/g has been sporadically reported.
- the magnitude of x in a carbonaceous material Li x Co varies with the proportion of graphite crystallites and can be manipulated by using different processing conditions, as exemplified in [Refs.1-4].
- An amorphous carbon phase alone tends to exhibit a low electrical conductivity (high charge transfer resistance) and, hence, a high polarization or internal power loss.
- Conventional amorphous carbon-based anode materials also tend to give rise to a high irreversible capacity.
- amorphous carbons commonly used as anode active materials are typically not purely amorphous, but contain some micro- or nano-crystallites with each crystallite being composed of a small number of graphene sheets (basal planes) that are stacked and bonded together by weak van der Waals forces.
- the number of graphene sheets varies between one and several hundreds, giving rise to a c-directional dimension (thickness Lc) of typically 0.34 nm to 100 nm.
- the length or width (La) of these crystallites is typically between tens of nanometers to microns.
- soft and hard carbons made by low-temperature pyrolysis exhibit a reversible capacity of 400-800 mAh/g in the 0-2.5 V range [Refs.1-3].
- Dahn et al. have made the so-called house-of-cards carbonaceous material with enhanced capacities approaching 700 mAh/g [Refs. 1,2].
- Tarascon's research group obtained enhanced capacities of up to 700 mAh/g by milling graphite, coke, or carbon fibers [Ref. 3].
- Peled and co-workers improved the reversible capacity of a graphite electrode to ⁇ 400 mAh/g by mild air oxidation [Ref. 4]. They showed that mild oxidation (burning) of graphite produces well-defined voids or nano-channels, having an opening of a few nanometers and up to tens of nanometers, on the surface of the graphite. They believed that these nano-channels were small enough to prevent co-intercalation of the solvent molecule but large enough to allow Li-ion penetration [Ref. 4]. These nano-channels were formed at the La-Lc interface, called "zigzag and armchair faces" between two adjacent crystallites, and in the vicinity of defects and impurities.
- Both natural and synthetic graphite materials typically have a wide variety of functional groups (e.g., carbonate, hydrogen, carboxyl, lactone, phenol, carbonyl, ether, pyrone, and chromene) at the edges of crystallites defined by La and Lc [Ref. 7]. These groups can react with lithium and/or electrolyte species to form a so-called in situ CB-SEI (chemically bonded solid electrolyte interface) [Ref. 4] on which, for example, carboxylic acid surface films are converted into Li-carboxylic salts.
- functional groups e.g., carbonate, hydrogen, carboxyl, lactone, phenol, carbonyl, ether, pyrone, and chromene
- These groups can react with lithium and/or electrolyte species to form a so-called in situ CB-SEI (chemically bonded solid electrolyte interface) [Ref. 4] on which, for example, carboxylic acid surface films are converted into Li-carboxylic salts
- lithium can occupy nearest neighbor sites; (ii) insertion of lithium species into nano-scaled cavities; (iii) in very disordered carbons containing large fractions of single graphene sheets (like the structure of a house of cards) lithium may be adsorbed on both sides of single layer sheets [Refs.
- inorganic materials that have been evaluated for potential anode applications include metal oxides, metal nitrides, metal sulfides, and the like, and a range of metals, metal alloys, and intermetallic compounds that can accommodate lithium atoms/ions.
- lithium alloys having a composition formula of Li a A (A is a metal such as Al, and "a" satisfies 0 ⁇ a # 5) has been investigated as potential anode materials.
- This class of anode material has a higher theoretical capacity, e.g., Li 4 Si (3,829 mAh/g), Li 44 Si (4,200 mAh/g), Li 44 Ge (1,623 mAh/g), Li 44 Sn (993 mAh/g), Li 3 Cd (715 mAh/g), Li 3 Sb (660 mAh/g), Li 44 Pb (569 mAh/g), LiZn (410 mAh/g), and Li 3 Bi (385 mAh/g).
- pulverization fragmentation of the alloy particles
- the expansion and contraction also tend to result in reduction in or loss of particle-to-particle contacts or contacts between the anode and its current collector.
- composites composed of small electrochemically active particles supported with less active or non-active matrices have been proposed for use as an anode material.
- active particles are Si, Sn, and Sn ⁇ 2 .
- most of prior art composite electrodes have deficiencies in some ways, e.g., in most cases, less than satisfactory reversible capacity, poor cycling stability, high irreversible capacity, ineffectiveness in reducing the internal stress or strain during the lithium ion insertion and extraction steps, and/or undesirable side effects.
- Kodas et al. provided carbon-metal particles by mixing the reactant, making the mixture into an aerosol, and then heating. Every particle contains a carbon phase and a metal phase.
- This study was primarily on carbon-supported platinum, silver, palladium, ruthenium, osmium and alloys thereof, which are for electro-catalysis purpose (e.g., for fuel cell applications).
- Hung disclosed a method of forming a composite anode material.
- the steps include selecting a carbon material as a constituent part of the composite, chemically treating the selected carbon material to receive nanoparticles, incorporating nanoparticles into the chemically treated carbon material, and removing surface nanoparticles from an outside surface of the carbon material with incorporated nanoparticles.
- a material making up the nanoparticles alloys with lithium.
- the resulting carbon/nanoparticle composite anodes did not exhibit any significant increase in capacity, mostly lower than 400 mAh/g.
- the prior art has not demonstrated a composite material that has all or most of the properties desired for use in an anode for the lithium-ion battery.
- a new anode for lithium-ion batteries that has a high cycle life, high reversible capacity, and low irreversible capacity.
- a method of readily or easily producing such a material is also a need for a method of readily or easily producing such a material.
- the present invention provides a negative electrode (anode) composite material composition for use in a lithium secondary battery.
- the composition comprises an electrochemically active material admixed with nano-scaled graphene platelets (NGPs), characterized in that both the active material and the NGPs are capable of absorbing and desorbing lithium ions.
- the electrochemically active material is in a fine powder form (smaller than 500 ⁇ m, preferably smaller than 200 ⁇ m, and most preferably smaller than 1 ⁇ m) and/or thin film (coating) form (preferably smaller than 100 nm in thickness), in contact with or attached to graphene platelets.
- An NGP is essentially composed of a sheet of graphene plane or multiple sheets of graphene plane stacked and bonded together through van der Waals forces.
- Each graphene plane also referred to as a graphene sheet or basal plane, comprises a two-dimensional hexagonal structure of carbon atoms.
- Each plate has a length and a width parallel to the graphite plane and a thickness orthogonal to the graphite plane.
- the thickness of an NGP is 100 nanometers (nm) or smaller, with a single-sheet NGP being as thin as 0.34 nm.
- the length and width of a NGP are typically between 1 :m and 20 ⁇ m, but could be longer or shorter.
- the NGPs form a myriad of electron transport paths for improving the electrical conductivity or reducing the internal resistance of the anode.
- the flexibility and strength of NGPs make them ideal materials to absorb or buffer the volume expansion or contraction of the electrochemically active material particles or coating.
- NGPs themselves are also capable of absorbing and extracting lithium (explained in a later section).
- the electrochemically active material in the present invention can be selected from the following groups of materials:
- a Silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), and cadmium (Cd); preferably of nanocrystalline or amorphous structure in a thin film (coating) or micron- or nanometer-sized particulate form.
- the coating is preferably thinner than 10 ⁇ m and more preferably thinner than 1 ⁇ m;
- SnO or Sn ⁇ 2 may be admixed with oxides of B, Al, P, Si, Ge, Ti, Mn, Fe, or Zn and then subjected to heat treatments to obtain composite oxides.
- Composite oxides may also be prepared by mechanical alloying (e.g., ball milling of a mixture of SnO and B 2 O3).
- SnO or Sn ⁇ 2 alone is of particular interest due to their high theoretical capacities. Iron oxide or phosphate is of interest since Li 6 Fe 2 O 3 has a theoretical capacity of 1,000 mAh/g.
- the first cycle capacity of Fe 3 PO? is found to reach 800 mAh/g.
- the capacity of SnS2 is as high as 620 mAh/g and is stable under charge-discharge cycling conditions, (d) Salts or hydroxides of Sn, e.g., SnSO 4 (with a reversible of 600 mAh/g), Sn 2 PO 4 Cl, (300 mAh/g even after 40 cycles), and Sn 3 O 2 (OH) 2 (300 mAh/g).
- amorphous carbon or polymeric carbon can be incorporated, in addition to any material in (a)-(d), in the exfoliated graphite host.
- the composite material (or its constituent active material and NGPs independently) may be mixed with a resin to form a precursor composite.
- This precursor composite may be heated at a temperature of typically 500-1,200 0 C to convert the resin into a polymeric carbon or an amorphous carbon phase.
- the composite material may further comprise an amorphous carbon phase or polymeric carbon.
- the amorphous carbon phase may be obtained from chemical vapor deposition, chemical vapor infiltration, or pyrolyzation of an organic precursor.
- the electrochemically active materials listed in (a)-(d) above when used alone as an anode material (with or without a polymer binder) in a particulate or thin film form, are found to suffer from the fragmentation problem and poor cycling stability.
- the resulting anode When mixed with the NGPs to form a composite material, the resulting anode exhibits a reversible capacity much higher than that of graphite (372 mAh/g), a low irreversible capacity loss, low internal resistance, and fast charge-recharge processes. It seems that NGPs, being mechanically flexible, are capable of accommodating or cushioning the strains or stresses induced by lithium insertion and extraction. With the active material particle size or coating thickness less than 1 ⁇ m, the distance for lithium ions to travel is reduced.
- the anode can quickly store or release lithium and thus can carry high current. This is a highly beneficial feature for a battery that is intended for high power density applications such as electric cars.
- NGPs also serve to separate or isolate active material particles from one another, preventing coalescence or sintering of fine particles. Furthermore, when the amount reaches a threshold volume fraction (percolation condition), NGPs form a continuous path for electrons, resulting in significantly reduced internal energy loss or internal heating.
- the nano-scaled graphene platelets may be obtained from intercalation, exfoliation, and separation of graphene sheets in a laminar graphite material selected from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, carbon fiber, carbon nano-fiber, graphitic nano-fiber, spherical graphite or graphite globule, meso-phase micro-bead, meso-phase pitch, graphitic coke, or polymeric carbon.
- natural graphite may be subjected to an intercalation/oxidation treatment under a condition comparable to what has been commonly employed to prepare the so-called expandable graphite or stable graphite intercalation compound (GIC).
- exfoliated graphite worms which are networks of interconnected exfoliated graphite flakes with each flake comprising one or a multiplicity of graphene sheets.
- the exfoliated graphite is then subjected to mechanical shearing (e.g., using an air milling, ball milling, or ultrasonication treatment) to break up the exfoliated graphite flakes and separate the graphene sheets ⁇ Refs. 36-49].
- mechanical shearing e.g., using an air milling, ball milling, or ultrasonication treatment
- These NGPs can be mixed with electrochemically active material particles, or the platelet surfaces may be deposited with a coating of the active material.
- exfoliated graphite worms and NGPs are quite distinct in structure, morphology, and properties.
- exfoliated graphite worms are characterized by having networks of largely interconnected graphite flakes having pores or empty pockets between flakes.
- the densities of worms are between 0.01 g/cm and 2.0 g/cm .
- These flakes have a typical length/width/diameter dimension of 0.5-100 ⁇ m (more typically 1-20 ⁇ m) and typical thickness of 0.34 nm - 500 nm (more typically 10-100 nm). These flakes are still physically attached to or chemically bonded to one another.
- the networks Upon separation and some further exfoliation of graphene sheets that constitute the flakes, the networks are broken, the flakes are separated, and some flakes are further split into thinner platelets.
- the NGPs typically are much thinner than their parent flakes and often smaller in length/width/diameter.
- Individual NGPs have a density of approximately 2.3 g/cm 3 .
- NGPs and graphite worms are patently distinct and, hence, the instant application is patently distinct from the co-pending application: Aruna Zhamu and Bor Z. Jang, "HYBRID ANODE COMPOSITIONS FOR LITHIUM ION BATTERIES," submitted to the US Patent and Trademark Office on the same day.
- a binder material may be used to further bond the particles together to produce an integral anode member.
- the binder material may be a non-conductive material, such as polyvinylidene fluoride (PVDF) and poly(tetrafluoroethylene) (PTFE).
- PVDF polyvinylidene fluoride
- PTFE poly(tetrafluoroethylene)
- An electrically conductive binder material may be selected from coal tar pitch, petroleum pitch, meso-phase pitch, coke, a pyrolized version of pitch or coke, or a conjugate chain polymer (intrinsically conductive polymer such as polythiophene, polypyrrole, or polyaniline.
- the present invention is a lithium secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte disposed between the negative electrode and the positive electrode.
- the anode (negative electrode) comprises a composite composition composed of an electrochemically active material admixed with NGPs, characterized in that both the active material and the NGPs are capable of absorbing and desorbing lithium ions.
- the active material can be in the form of fine particles or thin coating film.
- the anode material in the present invention provides a reversible specific capacity of typically greater than 600 mAh/g, often greater than 800 mAh/g, and, in many cases, much greater than 1,000 mAh/g (all based on per gram of composite material), which all far exceed the theoretical specific capacity of 372 mAh/g for graphite anode material. They also exhibit superior multiple-cycle behaviors with a small capacity fade and a long cycle life.
- FIG.1 Schematic of a cylinder-shape lithium ion battery.
- FIG.2 TEM micrographs of NGPs (several NGPs overlapping each other).
- FIG.3 Specific capacities of various anode materials: Sn-only, NGPs-only, theoretical model (based on a rule-of-mixture law), and Sn + NGPs.
- FIG.4 Specific capacities of Si thin film anode supported on NGPs and a baseline Si thin film anode supported on a Ni foil, respectively.
- FIG.5 Specific capacities of a (Sn+Li 2 O) mixture bonded by a resin binder and that supported by NGPs, respectively.
- FIG.6 Four sets of specific capacity data: Series 1 (denoted by ⁇ ) is for C-coated Si particles bonded by a resin binder with specific capacity calculated on the basis of per gram of Si (carbon weight not counted); Series 2 (denoted by D) is for C-coated Si particles hosted by 20% by weight of NGPs with specific capacity calculated on the basis of per gram of Si (carbon and graphene weights not counted); Series 3 (denoted by x) is for C-coated Si particles bonded by a resin binder with specific capacity calculated on the basis of per gram of (Si + C); and Series 4 (denoted by
- G is for C-coated Si particles hosted by 20% by weight of NGPs with specific capacity calculated on the basis of per gram of (Si + C + NGP).
- This invention is related to anode materials for high-capacity lithium secondary batteries, which are preferably secondary batteries based on a non-aqueous electrolyte or a polymer gel electrolyte.
- the shape of a lithium secondary battery can be cylindrical, square, button-like, etc.
- the present invention is not limited to any battery shape or configuration.
- a cylindrical battery configuration is shown in FIG. 1.
- a cylindrical case 10 made of stainless steel has, at the bottom thereof, an insulating body 12.
- An assembly 14 of electrodes is housed in the cylindrical case 10 such that a strip-like laminate body, comprising a positive electrode 16, a separator 18, and a negative electrode 20 stacked in this order, is spirally wound with a separator being disposed at the outermost side of the electrode assembly 14.
- the cylindrical case 10 is filled with an electrolyte.
- a sheet of insulating paper 22 having an opening at the center is disposed over the electrode assembly 14 placed in the cylindrical case 10.
- An insulating seal plate 24 is mounted at the upper opening of the cylindrical case 10 and hermetically fixed to the cylindrical case 10 by caulking the upper opening portion of the case 10 inwardly.
- a positive electrode terminal 26 is fitted in the central opening of the insulating seal plate 24.
- One end of a positive electrode lead 28 is connected to the positive electrode 16 and the other end thereof is connected to the positive electrode terminal 26.
- the negative electrode 20 is connected via a negative lead (not shown) to the cylindrical case 10 functioning as a negative terminal.
- the positive electrode (cathode) active materials are well-known in the art.
- the positive electrode 16 can be manufactured by the steps of (a) mixing a positive electrode active material with a conductor agent (conductivity -promoting ingredient) and a binder, (b) dispersing the resultant mixture in a suitable solvent, (c) coating the resulting suspension on a collector, and (d) removing the solvent from the suspension to form a thin plate-like electrode.
- the positive electrode active material may be selected from a wide variety of oxides, such as manganese dioxide, lithium/manganese composite oxide, lithium-containing nickel oxide, lithium-containing cobalt oxide, lithium-containing nickel cobalt oxide, lithium-containing iron oxide and lithium-containing vanadium oxide.
- Positive electrode active material may also be selected from chalcogen compounds, such as titanium disulfate or molybdenum disulfate. More preferred are lithium cobalt oxide (e.g., Li x CoCh where 0.8 ⁇ x ⁇ 1), lithium nickel oxide (e.g., LiNiCh), lithium manganese oxide (e.g., LiMn 2 ⁇ 4 and LiMnCh), lithium iron phosphate, lithium vanadium phosphate because these oxides provide a high cell voltage and good cycling stability.
- lithium cobalt oxide e.g., Li x CoCh where 0.8 ⁇ x ⁇ 1
- lithium nickel oxide e.g., LiNiCh
- lithium manganese oxide e.g., LiMn 2 ⁇ 4 and LiMnCh
- lithium iron phosphate lithium vanadium phosphate because these oxides provide a high cell voltage and good cycling stability.
- Acetylene black, carbon black, ultra-fine graphite particles, or NGPs may be used as a conductor agent in the cathode.
- the binder may be chosen from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), ethylene-propylene- diene copolymer (EPDM), or styrene-butadiene rubber (SBR), for example.
- Conductive materials such as electronically conductive polymers, meso-phase pitch, coal tar pitch, and petroleum pitch may also be used. Preferable mixing ratio of these ingredients may be 80 to 95% by weight for the positive electrode active material, 3 to 20% by weight for the conductor agent, and 2 to 7% by weight for the binder.
- the current collector may be selected from aluminum foil, stainless steel foil, and nickel foil. There is no particularly significant restriction on the type of current collector, provided the material is a good electrical conductor and relatively corrosion resistant.
- the separator may be selected from a synthetic resin nonwoven fabric, porous polyethylene film, porous polypropylene film, or porous PTFE film.
- the negative electrode (anode), which the instant invention provides, is now explained in detail as follows:
- the anode composition comprises an electrochemically active material admixed with nano-scaled graphene platelets (NGPs) (e.g. FIG.2). Both the electrochemically active material and the NGPs are capable of absorbing and desorbing lithium ions.
- NGPs nano-scaled graphene platelets
- Both the electrochemically active material and the NGPs are capable of absorbing and desorbing lithium ions.
- micron-sized in the present context is for those particles having a dimension ⁇ 500 ⁇ m or for a coating having a thickness ⁇ 500 ⁇ m.
- the electrochemically active material herein discussed is in a fine powder form (having a dimension in the range of 1 nm to 500 ⁇ m, more typically in the range of 10 nm to 200 ⁇ m) and/or thin film form (coating, typically in the range of 1 nm to 100 ⁇ m, but more typically in the range of 1 nm to 1 ⁇ m).
- An NGP is essentially composed of a sheet of graphene plane or multiple sheets of graphene plane stacked and bonded together through van der Waals forces.
- Each graphene plane also referred to as a graphene sheet or basal plane, comprises a two-dimensional hexagonal structure of carbon atoms.
- Each plate has a length and a width parallel to the graphite plane and a thickness orthogonal to the graphite plane.
- the thickness of an NGP is 100 nanometers (nm) or smaller, with a single-sheet NGP being as thin as 0.34 nm.
- the length and width of a NGP are typically between 1 :m and 20 ⁇ m, but could be longer or shorter.
- NGPs typically have a specific surface area greater than about 100 m 2 /gm when they have an average thickness thinner than 10 nm.
- the specific surface area can be greater than about 500 m /gm when they have an average thickness thinner than 2 nm.
- Single-sheet graphene has a theoretical specific surface area as high as 2,675 m 2 /gm.
- ⁇ GPs Since individual or fully separated ⁇ GPs do not have defect areas, such as inter-crystallite boundaries in natural graphite or graphitic carbons, ⁇ GPs should have a reversible capacity very close to the theoretical limit (372 mAh/g) for perfectly lithiated graphite, LiC ⁇ . With reduced platelet length and width and with all side surfaces (edges) of an ⁇ GP exposed to the electrolyte, the ⁇ GP enables fast, barrier-free diffusion of Li ions in and out of the interstices. This is conducive to fast charge and discharge of a secondary battery containing ⁇ GPs as an anode active material.
- Such a unique form factor enables a small number of ⁇ GPs dispersed in a matrix material to easily reach a percolation condition to ensure the formation of a network of electron-conducting paths. Theoretically, it is possible to use only ⁇ 1% by volume of ⁇ GPs to achieve percolation. However, to have a full capability of cushioning the volume change- induced stress or strains in a composite, more than 1% will be best. We recommend at least 5% by weight of ⁇ GPs in the composite anode.
- the electrochemically active material e.g., Si particles or film
- the ⁇ GPs can form a network of electron transport paths for dramatically improved electrical conductivity or reduced internal resistance (hence, reduced energy loss and internal heat build-up). It appears that the mechanical flexibility of ⁇ GPs enables them to buffer or accommodate the expanded or contracted volume of the particles or coating during the charge-discharge cycling of the lithium ion battery, thereby avoiding the fragmentation of the particles or coating, or loss of contact with the anode current collector.
- the electrochemically active material in the present invention is preferably selected from the following groups of materials: (1) Silicon (Si), germanium (Ge), tin (Sn), lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), and cadmium (Cd); preferably of nanocrystalline or amorphous structure in a thin film (coating) or micron- or nanometer-sized particulate form.
- the coating is preferably thinner than 10 ⁇ m and more preferably thinner than 1 ⁇ m; This group of material was chosen for our studies due to the notion that their theoretical capacity is significantly higher than that of graphite alone: Li 4-44 Si (3,829 - 4,200 mAh/g), Li 44 Ge (1,623 mAh/g), Li 44 Sn (993 mAh/g), Li 3 Cd (715 mAh/g), Li 3 Sb (660 mAh/g), Li 44 Pb (569 mAh/g), LiZn (410 mAh/g), and Li 3 Bi (385 mAh/g).
- Salts or hydroxides of Sn e.g., SnSO 4 (600 mAh/g), Sn 2 PO 4 Cl, (300 mAh/g even after 40 cycles), and Sn 3 O 2 (OH) 2 (300 mAh/g).
- the NGPs can be obtained from the intercalation, exfoliation, and separation of graphene sheets of a laminar graphite material, explained as follows: Carbon materials can assume an essentially amorphous structure (glassy carbon), a highly organized crystal (graphite crystal or crystallite), or a whole range of intermediate structures that are characterized by having various proportions and sizes of graphite crystallites and defects dispersed in an amorphous carbon matrix.
- a graphite crystallite is composed of a number of graphene sheets or basal planes (also referred to as a-b planes) that are bonded together through van der Waals forces in the c-axis direction, the direction perpendicular to the basal plane.
- graphite crystallites are typically micron- or nanometer-sized in the a- or ⁇ -direction (these are called La dimension).
- the c-directional dimension (or thickness) is commonly referred to as Lc.
- the interplanar spacing of a perfect graphite is known to be approximately 0.335 nm (3.35 ⁇ ).
- the graphite crystallites are dispersed in or connected by crystal defects or an amorphous phase in a laminar graphite particle, which can be a graphite flake (natural or synthetic, such as highly oriented pyrolytic graphite, HOPG), graphite spherule (spheroidal graphite or micro graphite ball), carbon/graphite fiber segment, carbon/graphite whisker, carbon/graphite nano-fiber (CNF or GNF), meso- phase micro-bead (MCMB).
- the graphene plates may be a part of a characteristic "turbostratic" structure.
- a laminar graphite material can be subjected to a chemical treatment (intercalation and/or oxidation) to form a graphite intercalation compound (GIC).
- GIC graphite intercalation compound
- the GIC is then exposed a thermal shock (at a high temperature, typically 800 - 1,050 0 C) for a short period of time (typically 15-60 seconds).
- the resulting products are networks of exfoliated graphite flakes commonly referred to as graphite worms.
- a graphite worm is characterized as having a network of largely interconnected exfoliated flaks with pores between flakes.
- the flakes have a typical length/width/diameter dimension of 0.5-100 ⁇ m (more typically 1-20 ⁇ m) and typical thickness of 0.34 nm - 500 nm (more typically 10-100 nm). These flakes in a graphite worm remain substantially interconnected (physically in contact with each other or bonded to each other). Hence, a mechanical shearing treatment is typically needed to break up the flakes to form separated or isolated NGPs.
- individual NGPs are basically graphite crystals that have a high in-plane electrical conductivity, up to 10 4 - 10 5 S/cm, which is orders of magnitude higher than that of carbon black, activated carbon, polymeric carbon, amorphous carbon, hard carbon, soft carbon, and meso-phase pitch, etc. This is particularly useful since an anode should have a low electrical resistance to reduce the energy loss.
- Individual NGPs have a density close to 2.3 g/cm .
- the resulting mixture upon mixing NGPs with an electrochemically active material, the resulting mixture may be subjected to re-compression to form an integral anode structure, in which the active material particles or coating are further held in place between NGPs (with or without a resin binder).
- the NGP amount is in the range of 2% to 90% by weight and the amount of particles or coating is in the range of 98% to 10% by weight. It may be noted that Greinke, et al., in US Pat. No.
- the NGPs are derived from natural graphite, synthetic graphite, highly oriented pyrolytic graphite, graphite fiber, carbon fiber, carbon nano-fiber, graphitic nano-fiber, spherical graphite or graphite globule, meso-phase micro-bead (MCMB), meso-phase pitch, graphitic coke, or polymeric carbon.
- natural flake graphite may be subjected to an electrochemical or chemical intercalation treatment under a condition comparable to what has been commonly employed to prepare the so- called expandable graphite or stable graphite intercalation compound.
- the resulting acid-intercalated graphite compound is then subjected to washing and rinsing and then dried to obtain expandable graphite.
- the expandable graphite is then heat- exfoliated and mechanically sheared to obtain NGPs.
- the spheroidal graphite produced by spheroidizing natural graphite flakes using a special thermo-chemical procedure, is available from several commercial sources (e.g., Huadong Graphite Co., Pingdu, China).
- the spheroidal graphite has a basically identical crystalline structure as in natural graphite, having relatively well-ordered crystallites with an interplanar spacing of 0.336 nm.
- the MCMB is obtained by extracting meso-phase particles out of other less-ordered carbon matrix and then graphitizing the meso-phase particles. They are typically supplied as a highly graphitic form of graphite.
- Commercial sources of MCMBs include Osaka Gas Company, Japan, China Steel Chemical Co., Taiwan, and Shanghai Shanshan Technology Co., China.
- the starting laminar graphite material preferably has a numerical particle size (measured by a laser scattering method) that is smaller than about 25 ⁇ m, more preferably smaller than about 10 ⁇ m, and most preferably smaller than about 5 ⁇ m.
- the smaller particle size leading to smaller NGPs, reduces lithium diffusion distances and increases the rate capability of the anode, which is a factor in preventing lithium plating at the anode.
- meso-phase pitch, graphitic coke, or polymeric carbon may require additional graphitization treatment, typically at a temperature in the range of 1,500 to 3,000 0 C to form nano- or micron-scaled graphite crystallites dispersed in an amorphous carbon matrix.
- Such a blend or composite of graphitic phase (graphite crystallites) and non-crystalline phase is then subjected to the same intercalation treatment to obtain an expandable graphite sample.
- the expandable graphite is then exposed to a thermal shock to obtain the exfoliated NGPs, which are the host material in the presently invented anode material.
- the electrochemically active particles or coating of an anode material include at least one of silicon (Si), germanium (Ge), and tin (Sn) as an element. This is because silicon, germanium, and tin have a high capability of inserting and extracting lithium, and can reach a high energy density.
- the next preferred group of elements includes lead (Pb), antimony (Sb), bismuth (Bi), zinc (Zn), aluminum (Al), and cadmium (Cd).
- an active material examples include the simple substance (metal element), an alloy, or a compound of silicon (Si), germanium (Ge), or tin (Sn), and combinations thereof.
- the active material may include only one kind or a mixture of a plurality of kinds selected from the group consisting of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, and Cd.
- the alloy or compound may include one or more kinds of metal elements from this group and one or more kinds of metal elements from other groups. Further, the alloy or compound may include a non-metal element.
- the active alloy or compound material may be a solid solution, a eutectic (eutectic mixture), an intermetallic compound (stoichiometric or non-stoichiometric), or the coexistence of two or more kinds selected from them.
- the material comprises a nanocrystalline or amorphous phase.
- an active material may include at least one element selected from the group consisting of tin (Sn), nickel (Ni), copper (Cu), iron (Fe), cobalt (Co), manganese (Mn), zinc (Zn), indium (In), silver (Ag), titanium, germanium (Ge), bismuth (Bi), antimony (Sb) and chromium (Cr) as a second element in addition to silicon.
- an active material may include at least one kind selected from the group consisting of silicon, nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium as a second element in addition to tin.
- a compound of silicon or a compound of tin for example, a compound including oxygen (O), carbon (C), nitrogen (N), sulfur (S), or phosphorous (P) may be used, and the compound may include the above-described second element in addition to tin or silicon.
- a preferred example is a SnCoC-containing material in which tin, cobalt and carbon are included as elements, and the carbon content is within a range from 9.9 wt % to 29.7 wt % inclusive, and the ratio Co/(Sn+Co) of cobalt to the total of tin and cobalt is within a range from 30 wt % to 70 wt % inclusive, because a high energy density and superior cycle characteristics can be obtained within such a composition range for an electrochemically active material hosted by exfoliated graphite flakes.
- the SnCoC-containing material may further include any other element, if necessary.
- the element for example, silicon, iron, nickel, chromium, indium, niobium (Nb), germanium, titanium, molybdenum (Mo), aluminum, phosphorus (P), gallium (Ga) or bismuth is preferable, and two or more kinds selected from them may be included. This suggestion is based on the observation that the capacity and the cycle characteristics of anodes can be further improved.
- the SnCoC-containing material includes a phase including tin, cobalt and carbon, and the phase preferably has a nano-crystalline structure or an amorphous structure.
- At least a part of carbon if added as an element is preferably bonded to a metal element or a metal compound. This is based on the consideration that a decline in the cycle characteristics of prior art lithium ion battery is caused by cohesion or crystallization of tin or the like. When carbon is bonded to the metal or compound, such cohesion or crystallization can be inhibited. However, we have observed that, with the active material hosted in the pores between exfoliated graphite flakes, there has been minimal or not cohesion or crystallization. Presumably, this is one of the major advantages of using exfoliated graphite flakes as a host.
- Such an electrochemically active material can be manufactured, for example, by simply mixing the materials of all elements to form a mixture, melting the mixture in an electric furnace, a high-frequency induction furnace, an arc furnace or the like, and then solidifying the mixture.
- the material may also be made by various atomization methods, such as gas atomization or water atomization, various roll methods, or methods using a mechanochemical reaction, such as a mechanical alloying method or a mechanical milling method.
- the active material is preferably manufactured by the method using a mechanochemical reaction, because the active material can have a low crystalline (or nano- crystalline) structure or an amorphous structure.
- a manufacturing apparatus such as a high energy planetary ball mill or a mechanical attritor can be used.
- the resulting fine particles are then mechanically blended with graphite worms in a dry blender or a solution/liquid mixer. In the later case, the liquid phase involved has to be removed.
- the active material in a thin film or coating form may be formed through depositing the material by, for example, a liquid-phase deposition method, an electrodeposition method, a dip coating method, an evaporation method, a sputtering method, a CVD (Chemical Vapor Deposition) method, or the like.
- the coating is preferably formed by the liquid-phase deposition method among them, because the deposition of an extremely small amount of the active material (e.g., SnO or Sn ⁇ 2) can be easily controlled.
- the liquid-phase deposition method is a method of depositing the metal oxide coating on a surface of graphite flakes.
- this can be accomplished by adding a dissolved species, which easily coordinates fluorine (F) as an anion trapping agent, into a metal fluoride complex solution, and immersing the exfoliated graphite flakes in the solution, and then trapping a fluorine anion generated from the metal fluoride complex by the dissolved species.
- a metal compound generating another anion such as a sulfate ion may be used.
- the sol-gel technique may be used to impregnate graphite worms and then subjected to final conversion to the fine particles, such as silicon dioxide, SiCh.
- Another preferred class of electrochemically active material that can be hosted by NGPs includes the oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or their mixtures (e.g., co-oxides or composite oxides) of Si, Ge, Sn, Pb, Sb, Bi, Zn, Al, Fe, or Cd. They can be readily produced in a fine powder or thin film form. For instance, SnO or SnCh may be admixed with oxides of B, Al, P, Si, Ge, Ti, Mn, Fe, or Zn and then subjected to heat treatments to obtain composite oxides.
- Composite oxides may also be prepared by mechanical alloying (e.g., ball milling of a mixture of SnO and B 2 O3).
- SnO or Sn ⁇ 2 alone is of particular interest due to their high theoretical capacities.
- Iron oxides or phosphates are of interest since LieFe 2 ⁇ 3 has a theoretical capacity of 1,000 mAh/g.
- the first cycle capacity of FesPO? is found to reach 800 mAh/g.
- the capacity of SnS 2 is as high as 620 mAh/g and is stable under charge-discharge cycling conditions.
- Combined atomization (or vaporization) and reaction can be used to obtain the oxides, carbides, nitrides, sulfides, phosphides, selenides, tellurides, or their mixtures, as illustrated in W. C. Huang, "Method for the Production of Semiconductor Quantum Particles," U.S. Patent No. 6,623,559 (Sept. 23, 2003) and J. H. Liu and B. Z. Jang, "Process and Apparatus for the Production of Nano-Scaled Powders," U.S. Patent No. 6,398,125 (June 4, 2002).
- U 3 N has a high lithium ion conductivity.
- a transition metal M such as Co, Ni, or Cu
- the U3N can be readily transformed into Li 3 _ x M x N.
- the nitride is transformed from a crystalline state to an amorphous state, resulting in a significant volume change. Due to the presence of NGPs, such a volume change did not lead to a volume change-induced failure of the anode and the anode appeared to provide a much better cycling response.
- an amorphous carbon phase may be added to the active material-NGP composite material in the following manner:
- the composite may be mixed with a resin to form a composite mixture.
- This composite mixture may be heated to a temperature of typically 500-1,000 0 C for a sufficient period of time to convert the resin into a polymeric carbon or an amorphous carbon phase.
- the composite material may further comprise an amorphous carbon phase or polymeric carbon, wherein the electrochemically active particles or coating may be bonded by an amorphous carbon phase or polymeric carbon.
- the amorphous carbon phase may be obtained from chemical vapor deposition (CVD), chemical vapor infiltration (CVI), or pyrolyzation of an organic precursor. CVD or CVI techniques are well-known in the art and have been utilized to cover a graphite material with an amorphous coating.
- the electrochemically active material if in fine powder form, may be further bonded by a binder material.
- An electrically conductive binder material may be selected from coal tar pitch, petroleum pitch, meso-phase pitch, coke, a pyrolized version of pitch or coke, or a conjugate chain polymer (intrinsically conductive polymer such as polythiophene, polypyrrole, or polyaniline.
- the particles may be bonded by a non-conductive material, such as polyvinylidene fluoride (PVDF) or PTFE, to form an integral anode member.
- PVDF polyvinylidene fluoride
- a wide range of electrolytes can be used for practicing the instant invention. Most preferred are non-aqueous and polymer gel electrolytes although other types can be used.
- the non-aqueous electrolyte to be employed herein may be produced by dissolving an electrolytic salt in a non-aqueous solvent. Any known non-aqueous solvent which has been employed as a solvent for a lithium secondary battery can be employed.
- a non-aqueous solvent mainly consisting of a mixed solvent comprising ethylene carbonate (EC) and at least one kind of non-aqueous solvent whose melting point is lower than that of aforementioned ethylene carbonate and whose donor number is 18 or less (hereinafter referred to as a second solvent) may be preferably employed.
- This non-aqueous solvent is advantageous in that it is (a) stable against a negative electrode containing a carbonaceous material well developed in graphite structure; (b) effective in suppressing the reductive or oxidative decomposition of electrolyte; and (c) high in conductivity.
- a non-aqueous electrolyte solely composed of ethylene carbonate (EC) is advantageous in that it is relatively stable against decomposition through a reduction by a graphitized carbonaceous material.
- the melting point of EC is relatively high, 39 to 40 0 C, and the viscosity thereof is relatively high, so that the conductivity thereof is low, thus making EC alone unsuited for use as a secondary battery electrolyte to be operated at room temperature or lower.
- the second solvent to be used in a mixture with EC functions to make the viscosity of the solvent mixture lower than that of EC alone, thereby promoting the ion conductivity of the mixed solvent. Furthermore, when the second solvent having a donor number of 18 or less (the donor number of ethylene carbonate is 16.4) is employed, the aforementioned ethylene carbonate can be easily and selectively solvated with lithium ion, so that the reduction reaction of the second solvent with the carbonaceous material well developed in graphitization is assumed to be suppressed. Further, when the donor number of the second solvent is controlled to not more than 18, the oxidative decomposition potential to the lithium electrode can be easily increased to 4 V or more, so that it is possible to manufacture a lithium secondary battery of high voltage.
- Preferable second solvents are dimethyl carbonate (DMC), methylethyl carbonate (MEC), diethyl carbonate (DEC), ethyl propionate, methyl propionate, propylene carbonate (PC), . gamma. -butyrolactone (.gamma. -BL), acetonitrile (AN), ethyl acetate (EA), propyl formate (PF), methyl formate (MF), toluene, xylene and methyl acetate (MA).
- DMC dimethyl carbonate
- MEC methylethyl carbonate
- DEC diethyl carbonate
- ethyl propionate methyl propionate
- PC propylene carbonate
- AN gamma. -butyrolactone
- AN acetonitrile
- EA ethyl acetate
- PF propyl formate
- MF methyl formate
- MA toluen
- the mixing ratio of the aforementioned ethylene carbonate in the mixed solvent should preferably be 10 to 80% by volume. If the mixing ratio of the ethylene carbonate falls outside this range, the conductivity of the solvent may be lowered or the solvent tends to be more easily decomposed, thereby deteriorating the charge/discharge efficiency. More preferable mixing ratio of the ethylene carbonate is 20 to 75% by volume. When the mixing ratio of ethylene carbonate in a non-aqueous solvent is increased to 20% by volume or more, the solvating effect of ethylene carbonate to lithium ions will be facilitated and the solvent decomposition-inhibiting effect thereof can be improved.
- Examples of preferred mixed solvent are a composition comprising EC and MEC; comprising EC, PC and MEC; comprising EC, MEC and DEC; comprising EC, MEC and DMC; and comprising EC, MEC, PC and DEC; with the volume ratio of MEC being controlled within the range of 30 to 80%.
- the volume ratio of MEC from the range of 30 to 80%, more preferably 40 to 70%, the conductivity of the solvent can be improved.
- an electrolyte having carbon dioxide dissolved therein may be employed, thereby effectively improving both the capacity and cycle life of the battery.
- the electrolytic salts to be incorporated into a non-aqueous electrolyte may be selected from a lithium salt such as lithium perchlorate (LiClO 4 ), lithium hexafluorophosphate (LiPFe), lithium borofluoride (LiBF 4 ), lithium hexafluoroarsenide (LiAsF 6 ), lithium trifluoro-metasulfonate (LiCF 3 SOs) and bis-trifluoromethyl sulfonylimide lithium [LiN(CF 3 SO 2 ) 2 ].
- LiPF 6 , LiBF 4 and LiN(CF 3 SO 2 ) 2 are preferred.
- the content of aforementioned electrolytic salts in the non-aqueous solvent is preferably 0.5 to 2.0 mol/1.
- raw materials such as silicon, germanium, bismuth, antimony, zinc, iron, nickel, titanium, cobalt, and tin were obtained from either Alfa Aesar of Ward Hill, Mass., Aldrich Chemical Company of Milwaukee, Wis. or Alcan Metal Powders of Berkeley, CA.
- X-ray diffraction patterns were collected using a Siemens diffractometer equipped with a copper target x-ray tube and a diffracted beam monochromator. The presence or absence of characteristic patterns of peaks was observed for each of the alloy samples studied. For example, a phase was considered to be amorphous when the X-ray diffraction pattern was absent or lacked sharp, well-defined peaks.
- the grain sizes of the crystalline phases were determined by the Scherer equation. When the grain size was calculated to be less than 50 nanometers, the phase was considered to be nanocrystalline. In several cases, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used to characterize the structure and morphology of the hybrid material samples.
- SEM scanning electron microscopy
- TEM transmission electron microscopy
- each of the electrochemically active materials alone (without being hosted by NGPs) was formed into an electrode and characterized in an electrochemical cell.
- the corresponding composite material was also separately incorporated into a lithium ion battery as an anode.
- the powder particles obtained in the Comparative Samples were separately mixed with, as a binder, 2.2% by weight of styrene/butadiene rubber and 1.1% by weight of carboxylmethyl cellulose to obtain a mixture (a precursor to an anode active material), which was then coated on a copper foil to be employed as a collector. After being dried, the powder/resin mixture-copper foil configuration was hot-pressed to obtain a negative electrode.
- PVDF particles were used as a binder material.
- Powder particles may also be bonded by an electronically conductive polymer.
- polyaniline-maleic acid-dodecyl hydrogensulfate salt may be synthesized directly via emulsion polymerization pathway using benzoyl peroxide oxidant, sodium dodecyl sulfate surfactant, and maleic acid as dopants.
- Dry polyaniline-based powder may be dissolved in DMF up to 2% w/v to form a solution.
- the cathode of a lithium ion battery was prepared in the following way. First, 91% by weight of lithium cobalt oxide powder LiCoC ⁇ , 3.5% by weight of acetylene black, 3.5% by weight of graphite, and 2% by weight of ethylene- propylene-diene monomer powder were mixed together with toluene to obtain a mixture. The mixture was then coated on an aluminum foil (30 ⁇ m) serving as a current collector. The resulting two-layer aluminum foil-active material configuration was then hot-pressed to obtain a positive electrode.
- a positive electrode, a separator composed of a porous polyethylene film, and a negative electrode was stacked in this order.
- the stacked body was spirally wound with a separator layer being disposed at the outermost side to obtain an electrode assembly as schematically shown in FIG.1.
- Hexafluorolithium phosphate (LiPF ⁇ ) was dissolved in a mixed solvent consisting of ethylene carbonate (EC) and methylethyl carbonate (MEC) (volume ratio: 50:50) to obtain a non-aqueous electrolyte, the concentration Of LiPF 6 being 1.0 mol/1 (solvent).
- the electrode assembly and the non-aqueous electrolyte were placed in a bottomed cylindrical case made of stainless steel, thereby obtaining a cylindrical lithium secondary battery.
- Natural flake graphite nominally sized at 45 ⁇ m, provided by Asbury Carbons (405 Old Main St., Asbury, NJ 08802, USA) was milled to reduce the size to approximately 14 ⁇ m (Sample 1).
- the chemicals used in the present study including fuming nitric acid (> 90%), sulfuric acid (95-98%), potassium chlorate (98%), and hydrochloric acid (37%), were purchased from Sigma-Aldrich and used as received.
- a reaction flask containing a magnetic stir bar was charged with sulfuric acid (360 mL) and nitric acid (180 mL) and cooled by immersion in an ice bath. The acid mixture was stirred and allowed to cool for 15 min, and graphite (20 g) was added under vigorous stirring to avoid agglomeration. After the graphite powder was well dispersed, potassium chlorate (110 g) was added slowly over 15 min to avoid sudden increases in temperature. The reaction flask was loosely capped to allow evolution of gas from the reaction mixture, which was stirred for 48 hours at room temperature. On completion of the reaction, the mixture was poured into 8 L of deionized water and filtered. The slurry was spray-dried to recover an expandable graphite sample.
- the dried, expandable graphite was quickly placed in a tube furnace preheated to 1,000 0 C and allowed to stay inside a quartz tube for approximately 40 seconds to obtain exfoliated graphite worms.
- the worms were then subjected to an ultrasonication treatment (80 W for one hour) for flake break-up and separation of graphene sheets to obtain NGPs.
- a Branson S450 Ultrasonicator was used.
- Sample Ia Approximately 5 grams of the NGPs thus prepared were mixed with 25 grams of SnCl 2 in a glass flask under nitrogen environment. The mixture was heated at 370 0 C for approximately 10 hours. The product was rinsed in distilled water for one minute and then dried in ambient air for one hour. The dried product was post-heated at 1,000 0 C for one hour, resulting in a product that is composed of approximately 55% by weight Sn nanoparticles disposed in pores of the graphite worms.
- Comparative Sample Ia Sn nano particles were prepared in a similar manner without the presence of NGPs. These particles were bonded by a binder material (2.2% by weight of styrene/butadiene rubber and 1.1% by weight of carboxyl methyl cellulose) in the preparation of an anode member. NGPs with a binder material but without the Sn particles, were also made by re-compression into a baseline anode material.
- Sample Ib About 5 grams of Si powder were put in a tungsten heating boat. Approximately 5 grams of NGPs supported by a quartz plate of 30 cm x 5 cm and the Si- loaded tungsten boat were mounted in a vacuum chamber, which was evacuated to and maintained at a pressure of 10 "7 torr for 3 hours at room temperature. An electric current was passed directly on the tungsten boat to heat the loaded Si up to slightly above its melting point. The evaporation was controlled by monitoring the deposited thickness with a quartz crystal microbalance mounted near the graphite worm plate. The deposition rate was controlled to be about 2 A/min. The resulting product was a hybrid material containing a Si thin film coating on NGPs.
- Comparative Sample Ib The Si thin film was coated onto a surface of a 30 ⁇ m thick Ni foil and the resulting Si-coated Ni foil was used as an anode in a lithium ion battery. The Si-coated foil was cut into 1 cm x 1 cm squares with a Ni lead wire spot- welded thereon. The electrolyte used was 1 M LiClO 4 dissolved in propylene carbonate (PC). A Pyrex cylindrical cell with three electrodes was used to evaluate constant-current charge-discharge cycling behaviors, wherein pure metallic Li foils were used as the reference and counter electrodes.
- PC propylene carbonate
- NGPs for Samples 2a, 2b, 2c, 2d, and 2e were prepared according to the same procedure used for Sample 1 , but the starting graphite materials were highly oriented pyro lytic graphite (HOPG), graphite fiber (Amoco P-IOO graphitized carbon fiber), graphitic carbon nano-fiber (Pyrograph-III from Applied Science, Inc., Cedaville, Ohio), spheroidal graphite (HuaDong Graphite, QinDao, China), and meso-carbon micro-beads (MCMBs) (MCMB 2528, Osaka Gas Company, Japan), respectively.
- HOPG highly pyro lytic graphite
- graphite fiber Amoco P-IOO graphitized carbon fiber
- graphitic carbon nano-fiber Panograph-III from Applied Science, Inc., Cedaville, Ohio
- spheroidal graphite HuaDong Graphite, QinDao, China
- MCMBs
- the active materials may be prepared according to the following steps: (1) stanous oxide (SnO) powder and lithium nitride (Li 3 N) powder were mixed in a stoichiometric ratio of two moles Of Li 3 N to three moles of SnO; (2) the mixture of powders from step (1) was fed into a planetary ball mill (Model PM-400 from Glen Mills, Clifton, NJ), and the milling was proceeded until the SnO and Li 3 N reached a state characterized by complete disappearance of the X-ray diffraction patterns for crystalline SnO and Li 3 N, and the subsequent appearance of the X-ray patterns for amorphous Li 2 O and crystalline Sn.
- the ball milling process typically lasts for one to two days at ambient temperature; and (3) The milled powder was then blended with NGPs obtained in Sample 2a (i.e., from the HOPG) and the resulting powder mixture was press-rolled to form an anode layer of approximately 200 ⁇ m.
- the layer is composed of approximately 72% by weight of the Li 2 O-Sn mixture and 28% by weight of NGPs.
- the Comparative Sample 2a was prepared from the Li 2 O-Sn mixture powder bonded with approximately 5% resin binder.
- Samples 2b-2e were obtained from Pb, Ge, Si, and Cd, respectively as an electrochemically active material used in combination with NGPs from the graphite fiber, graphitic carbon nano-fiber (GNF), spheroidal graphite (SG), and MCMB, respectively.
- Comparative Samples 2a-2e were obtained from similarly made powder mixtures, which were not hosted by NGPs, but instead only bonded by a resin binder in the preparation of an anode.
- Additional graphite intercalation compound was prepared by intercalation and oxidation of natural graphite flakes (original size of 200 mesh, from Huadong Graphite Co., Pingdu, China, milled to approximately 15 ⁇ m, referred to as Sample 3a) with sulfuric acid, sodium nitrate, and potassium permanganate according to the method of Hummers [US Pat. ⁇ o.2, 798,878, July 9, 1957].
- Sample 3a sulfuric acid, sodium nitrate, and potassium permanganate according to the method of Hummers [US Pat. ⁇ o.2, 798,878, July 9, 1957].
- a mixture of 22 ml of concentrated sulfuric acid 2.8 grams of potassium permanganate, and 0.5 grams of sodium nitrate.
- the graphite flakes were immersed in the mixture solution and the reaction time was approximately one hour at 30 0 C.
- potassium permanganate should be gradually added to sulfuric acid in a well-controlled manner to avoid overheat and other safety issues.
- the mixture was poured into deionized water and filtered.
- the sample was then washed repeatedly with deionized water until the pH of the filtrate was approximately 5.
- the slurry was spray-dried and stored in a vacuum oven at 60 0 C for 24 hours.
- the resulting GIC was exposed to a temperature of 1,050 0 C for 35 seconds in a quartz tube filled with nitrogen gas to obtain worms of exfoliated graphite flakes.
- the worms were then subjected to an ultrasonication treatment (85 W for one hour) for flake break-up and separation of graphene sheets to obtain NGPs.
- the electrochemically active particles in these examples are Si x Sn q M y C z type compositions with (q+x) > (2y+z), x > 0, and M is one or more metals selected from manganese, molybdenum, niobium, tungsten, tantalum, iron, copper, titanium, vanadium, chromium, nickel, cobalt, zirconium, yttrium, or combinations thereof, wherein the Si, Sn, M, and C elements are arranged in the form of a multi-phase microstructure comprising at least one amorphous or nanocrystalline phase.
- Sample 3 a was prepared by ball-milling silicon chips, cobalt powder, and graphite powder with 28 tungsten carbide balls ( 5/16-inches each, approximately 108 grams) for 4 hours in a 45 milliliter tungsten carbide vessel using a planetary ball mill (Model PM-400 from Glen Mills, Clifton, NJ) under an argon atmosphere. The vessel was then opened, chunks of caked powder were broken up, and the milling was continued for an additional hour in an argon atmosphere. The temperature of the tungsten carbide vessel was maintained at about 30 0 C by air cooling. The product was determined to be approximately Si73C ⁇ 2 3C 4 .
- Samples 3b and 3c were prepared by the same general procedure as Sample 3a with the following differences. Silicon powder (325 mesh), tin powder ( ⁇ 10 microns), and Co or Ni metal powders (Cobalt, 1.6 microns; Nickel, Alcan Metal Powder, Type 123) were used. Samples 3b and 3c were milled with 14 tungsten carbide balls (0.415 mm diameter; approximately 54 grams total weight) in the ball mill for 16 hours in an argon atmosphere. The resulting products were Si74Sn 2 C ⁇ 24 and Si73Sn 2 Ni25, respectively.
- Samples 3a-3c the fine powder products prepared after ball milling were separately mixed with NGPs, plus 2% by weight of a resin binder, and then cold- compressed with a hydraulic press at 100 psig to prepare an anode sheet of approximately 200 ⁇ m in thickness.
- Comparative Samples 3a-3c the fine powder products were not hosted by NGPs, but instead only bonded by a resin binder in the preparation of an anode.
- the reversible capacities of Samples 3a, 3b, and 3c after 40 cycles were 1,160, 1222, 1213 mAh/g, respectively.
- the reversible capacities of Comparative Samples 3 a, 3b, and 3c after only 10 cycles were 782, 740, 892 mAh/g, respectively.
- Example 5a Nano-crystalline Si with an average particle size of 80 nm was produced in our laboratory using a twin-arc evaporation technique. Carbon-coated Si was prepared by a thermal vapor decomposition (TVD ) technique. The nano powder was supported on a quartz plate positioned inside a reaction tube. Benzene vapor and nitrogen gas were fed into the reaction tube (1 ,00O 0 Cj at flow rates of 2 niL/min and ! L/n ⁇ n, respectively. At such a high temperature, the organic vapor decomposed and carbon deposited onto the surface of Si particles.
- TVD thermal vapor decomposition
- the mean particle size of the carbon-coated silicon was found to be approximately 84 nm (approximately 13% by weight carbon). Carbon-coated Si particles were dry-blended with to produce a composite material designated as Sample 5a. The corresponding anode material bonded by a resin binder, without the presence of the ISIGP, is designated as Comparative Sample 5a.
- carbon-coated Si has been investigated as a potential lithium ion battery material, for instance, by a research group at Kyoto University: f. Uracno, et al., "Novel Anode Materials for Lithium-Ion Batteries: Carbon- Coated Silicon Prepared by Thermal Vapor Decomposition,' " Chemistry Letters (2001) 1186-1187 and M. Yoshio, et al., “Carbon-Coated Si as a Lithium-Ion Battery Anode Material," Journal of the Electrochemical Society, 149 (12) (2002) A1598-A1603.
- Series 1 (denoted by ⁇ ) is for C-coated Si particles bonded by a resin binder with specific capacity calculated on the basis of per gram of Si (carbon weight not counted);
- Series 2 (denoted by D) is for C- coated Si particles hosted by 20% by weight of NGPs with specific capacity calculated on the basis of per gram of Si (carbon and NGP weights not counted);
- Series 3 (denoted by x) is for C-coated Si particles bonded by a resin binder with specific capacity calculated on the basis of per gram of (Si + C);
- Series 4 (denoted bye) is for C-coated Si particles hosted by 20% by weight of NGPs with specific capacity calculated on the basis of per gram of (Si + C + NGP).
- a comparison between Series 1 and Series 2 data indicates that the NGP host enables the carbon-coated Si particles to provide a much better cycling performance. Furthermore, a comparison between Series 3 and Series 4 data indicates that, even after the additional NGP weight is taken into consideration, the C-coated Si hosted by the NGP provides a higher absolute specific capacity than the carbon-coated Si particles without an NGP host after 7 charge-discharge cycles.
- Example 6 The same batch of NGPs prepared in Example 3 was used in Example 6.
- Sample 6a Nano-SnSb alloy was deposited on the surfaces of (NGPs + CNFs) at a weight ratio of 3:7. Between NGPs and CNFs, we had 80% by weight of NGP particles + 20% by weight of CNF (Applied Sciences, inc.). CNFs were added to impart additional mechanical integral ty to the anode (without adding a resin binder).
- SbCl3 and SnCl 2 .H 2 O (99%) were mixed together with a molar ratio of 5:4 and dissolved in glycerin to form a 0.5 M solution. Then, NGP+CNF particles were added to the solution. The mixed solution or suspension was cooled down to 0.0 to 1.0 0 C. Zn powder (99.9%) with 95% stoichiometric amount was added to the solution gradually and stirred simultaneously. Finally, after washing by ethanol and filtering, the product was dried under vacuum at 55°C.
- Comparative Samples 6a nano-SnSb particles, without NGPs /CNFs, were prepared in a similar manner.
- the fine powder products were not hosted by NGPs, but instead just bonded by a resin binder in the preparation of an anode.
- the extent of irreversibility of Samples 6a was found to be 5.2% and, in contrast, the extent of irreversibility of Comparative Samples 6a was 21.5% after 100 cycles.
- Sample 6b Sn nano particles were prepared by a reduction method in glycerin solution at low temperature, SbCl3 was dissolved in glycerin to form a 0.5 M solution. Then, NGPs were added to the solution to form a suspension. The suspension was cooled to 0.0 to 1.0 0 C. Subsequently, Zn powder with a 95% stoichiometric amount was slowly added to the solution while being stirred. Finally, after washing with ethanol and filtering, the black product was dried under vacuum at 50 0 C. The product was a composite material containing Sn nano particles well mixed with NGPs, which were then compressed.
- Comparative Samples 6b nano-SnSb particles, without NGPs, were prepared in a similar manner.
- the fine powder products were not hosted by NGPs, but instead just bonded by a resin binder in the preparation of an anode.
- the extent of irreversibility of Samples 6a was found to be 5.5% and, in contrast, the extent of irreversibility of Comparative Samples 6a was 25.5% after 100 cycles.
- Sample 6c The Ni-Sn-P/graphene composite material was prepared by an electroless plating method in an aqueous solution.
- Sample 6d The starting materials for preparation of SnS nanoparticles included tin (II) chloride (SnCl 2 • 2H 2 O), sodium sulfide hydrate (Na 2 S 9H 2 O), and ethylene glycol (C 2 H 6 O 2 ).
- tin (II) chloride SnCl 2 • 2H 2 O
- sodium sulfide hydrate Na 2 S 9H 2 O
- ethylene glycol C 2 H 6 O 2
- 1.07 g sodium sulfide hydrate and 1.0 g tin (II) chloride were separately dissolved in an adequate amount of ethylene glycol by magnetic stirring. Then the tin (II) chloride solution was added into the sodium sulfide hydrate solution drop by drop with slow stirring. Upon dropping, the solution gradually turned from translucent to dark, indicating the formation of SnS particles. All operations above were conducted at higher than 6O 0 C.
- NGP particles were then added to the reacting solution. After complete mixing, the obtained solution was thermostated at 150 0 C for 24 h. Finally, brown black SnS/NGP particles were collected by centrifugation, washed with de-ionized water and dried at 80 0 C for 1 day.
- Comparative Samples 6d nano-SnS particles, without NGPs, were prepared in a similar manner.
- the fine powder products were not hosted by NGPs, but instead just bonded by a resin binder in the preparation of an anode.
- the extent of irreversibility of Samples 6d was found to be 5.6 and, in contrast, the extent of irreversibility of Comparative Samples 6d was 22.5% after 100 cycles.
- Sample 6e For the synthesis of carbon aerogel, resorcinol (CeH 6 O 2 ), formaldehyde (CH 6 O) and NH 3 H 2 O were used. Resorcinol and formaldehyde with a mole ratio of 1:2 were put into de-ionized water and agitated. Then, NH3 H 2 O was added to the resulting solution to adjust the pH value to 6.5. Afterwards, the resorcinol-formaldehyde solution was placed in thermostated container at 85°C.
- Sample 6f The spray pyrolysis technique was applied to synthesize in situ a series of SnO 2 -carbon nano-composites at 700 0 C.
- the in situ spray pyrolysis process ensures that the chemical reaction is completed during a short period of time, preventing the crystals from growing too large.
- a solution of SnCl 2 -2H 2 O and sucrose was used as a spray precursor.
- the spray precursors were prepared by mixing saturated aqueous sucrose solutions with tin (II) chloride dehydrate (Aldrich, 98%) IM ethanol solution, in SnCl 2 -2H 2 O/sucrose in weight ratios of 100:0, 60:40, 40:60, and 10:90, respectively.
- the SnO 2 pure sample and SnO 2 -carbon composites were obtained in situ using a vertical type of spray pyrolysis reactor at 700 0 C. The process resulted in super fine nanocrystalline SnO 2 , which was distributed homogeneously inside the amorphous carbon matrix.
- the C- SnO 2 composite particles were dry-blended with approximately 23% NGP particles and then slightly compressed to obtain Sample 6f.
- the anode material without NGPs was denoted as Comparative Sample 6f.
- the extent of irreversibility of Samples 6f was found to be 6.7 and, in contrast, the extent of irreversibility of Comparative Samples 6f was 27.5% after 100 cycles.
- Nanostructured CO3O 4 C and CO3O 4 powders were prepared in separate experiments using a vertical spray pyrolysis apparatus.
- the CO3O 4 powders was obtained by spraying aqueous 0.2 M cobalt nitrate solutions at ambient temperature through an ultrasonic nozzle at 3 mL/min into an open air 2 m quartz tube at 600 0 C.
- the precursor solution contained 0.05 M sucrose and 0.2 M cobalt nitrate.
- the experimental conditions for pyrolysis of this solution were identical to those described for CO3O 4 powder.
- the compositions of all final powder products were confirmed by X-ray diffraction (XRD).
- the CO3O 4 -C and CO3O 4 powders were separately dried blended with NGPs to obtain Samples 7a and 7b, respectively.
- the corresponding anodes, without NGPs but with a resin binder are denoted as Comparative Samples 7a and 7b, respectively.
- the extent of irreversibility of Samples 7a was found to be 6.3 %, and, in contrast, the extent of irreversibility of Comparative Samples 6a was 24.8% after 100 cycles.
- the extent of irreversibility of Samples 7b was found to be 6.4% and, in contrast, the extent of irreversibility of Comparative Samples 6a was 27.3% after 100 cycles.
- the present invention provides an innovative, versatile platform materials technology that enables the design and manufacture of superior anode materials for lithium ion batteries or other types of rechargeable batteries.
- This new technology appears to have the following advantages:
- the invented hybrid anode exhibits a reversible capacity much higher than that of graphite (372 mAh/g) and a low irreversible capacity loss.
- NGPs being mechanically flexible, are capable of accommodating or cushioning the strains or stresses induced by volume changes during lithium insertion and extraction.
- the distance for lithium ions to travel is reduced.
- the anode can quickly store or release lithium and thus can carry high current. This is a highly beneficial feature for a battery that is intended for high power density applications such as electric cars.
- the NGPs also serve to separate or isolate active material particles from one another, preventing coalescence or sintering of fine particles. Furthermore, with a sufficient amount of NGPs that reach a state of percolation, the highly conductive platelets form a continuous path for electrons, resulting in significantly reduced internal energy loss or internal heating.
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KR101266022B1 (en) | 2013-05-21 |
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US7745047B2 (en) | 2010-06-29 |
JP2011503804A (en) | 2011-01-27 |
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US20090117467A1 (en) | 2009-05-07 |
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